Anhydrous and water resistant cosmetic compositions

ABSTRACT

An anhydrous, water-resistant cosmetic composition comprising silicone-containing materials, fillers and pigments. This composition may be used as a make-up product or as a hair product.

This application is a continuation of application Ser. No. 08/538,046,filed Oct. 2, 1995, now abandoned.

The invention is directed to anhydrous and water-resistant make-upcompositions comprising, inter alia, at least one silicone gum.

Water-resistant compositions in water-in-oil or water-in-siliconeemulsion form are known in the prior art. The use of such emulsionsrelies on the fact that after spreading, the water evaporates and theoil or the silicone remains in contact with the skin, giving awater-resistant make-up. However, the application of such compositionshas the drawback of leaving the skin with an oily appearance and ofgiving a greasy feel. The result obtained after application is notreally natural, and the make-up shines or becomes shiny.

Another form of water-resistant cosmetic compositions is a compositionin which fillers, including pigments, are introduced into a volatile ornon-volatile silicone oil. The major drawback of this type ofcomposition lies in the stretching effect on the skin, and in theunpleasant, dry sensation which appears after application. Furthermore,the effect sought in the use of such compositions containing pigments,namely a coloration of the skin, is often not achieved. The very natureof the composition is such that the distribution of the pigments in thecomposition after spreading is not homogeneous; the pigments spread moreor less uniformly and tend to agglomerate in the pores and the folds inthe skin. This effect runs counter to the search for a coloration closeto that obtained naturally.

In all cases, the compositions obtained have faults both with regard tothe stability and with regard to the homogeneity of the dispersion ofthe pigments. Solutions to these problems have been proposed, such as,for example, the use of water-soluble dyes or of dihydroxyacetone (DHA).In the case of water-soluble dyes, the make-ups obtained are notwater-resistant and are not perfectly homogeneous.

Products using DHA are difficult to formulate, on account of thedegradation and the incompatibility of DHA with many components usuallyused in compositions of this type. In addition, a major drawback of DHA,in its use in cosmetic compositions, lies in the development ofunpleasant odors during ageing.

An object of the present invention is to provide solutions to thevarious problems encountered in the applications of the prior art and topropose a cosmetic composition possessing good water resistance and atthe same time possessing good cosmetic properties.

The Inventors have been able to show, surprisingly and unexpectedly,that it is possible to obtain anhydrous, water-resistant make-upcompositions which are highly homogeneous in particular with regard tospreading, by mixing together pigments and at least a large proportionof silicone gum and a silicone oil.

More particularly, a subject of the present invention is an anhydrous,water-resistant cosmetic composition preferably comprising from 2 to 50%of at least one silicone gum, from 10 to 90% of at least one siliconeoil, from 0.5 to 15% of at least one pigment and from 0 to 30% of atleast one filler.

The compositions according to the invention have the advantage of beingstable over time. They are water-resistant since they are anhydrous, anddo not contain any water-soluble dyes or solvent. They also have goodstaying power and do not cause any pulling effect on the skin.

It has furthermore been observed, surprisingly, that the pigmentspresent in the compositions according to the invention were dispersedtherein in an unexpectedly very homogeneous manner. This thus has theadditional advantage of giving a very uniform and very homogeneousmake-up of the skin.

In the following text, the percentages will always be given by weight ofactive material relative to the total weight of the composition.

In the compositions according to the invention, the silicone gum ispreferably present in a proportion ranging from 2% to 50%, morepreferably ranging from 4 to 15% and still more preferably ranging from6% to 9%.

The silicone gum preferably has a molecular weight not greater than1,500,000. More preferably, the silicone gum has a molecular weightranging from 200,000 to 1,000,000.

The silicone gum preferably corresponds to the formula: ##STR1## inwhich:

R1, R2, R5, and R6 each independently represents an alkyl radical havingfrom 1 to 6 carbon atoms;

R3 and R4 each independently represents an alkyl radical having from 1to 6 carbon atoms or an aryl radical;

X represents an alkyl radical having from 1 to 6 carbon atoms, ahydroxyl radical or a vinyl radical;

n and p are chosen so as to give the silicone gum a viscosity preferablyof greater than 100,000 mPa s, and more preferably of greater than500,000 mPa s.

In general, n and p may have values preferably ranging from 0 to 5000,and more preferably ranging from 0 to 3000.

As silicone gum which may be used according to the invention, there maypreferably be mentioned those for which:

the substituents R1 to R6 and X represent a methyl group, p=0 andn=2700, such as that sold under the name SE30 by the company GeneralElectric;

the substituents R1 to R6 and X represent a methyl group, p=0 andn=2300, such as that sold under the name AK 500000 by the companyWacker;

the substituents R1 to R6 represent a methyl group, the substituent Xrepresents a hydroxyl group, p=0 and n=2700, in solution at aconcentration of 13% in cyclopentasiloxane, such as that sold under thename Q2-1401 by the company Dow Corning;

the substituents R1 to R6 represent a methyl group, the substituent Xrepresents a hydroxyl group, p=0 and n=2700, in solution at aconcentration of 13% in polydimethylsiloxane, such as that sold underthe name Q2-1403 by the company Dow Corning;

the substituents R1, R2, R5, R6 and X represent a methyl group and thesubstituents R3 and R4 represent an aryl group and p and n are such thatthe molecular weight of the compound is 600,000, such as that sold underthe name 761 by the company Rhone-Poulenc.

The composition according to the invention preferably also comprises atleast one silicone oil, in a proportion preferably ranging from 10 to90%.

A volatile or non-volatile silicone oil may be used.

There may be mentioned, for example:

cyclomethicones D4, D5, D6;

polydimethylsiloxanes (PDMS) of viscosity preferably less than 100 mPa sand more preferably less than 10 mPa s;

alkyldimethicones such as X2-1731 from Dow Corning corresponding to theformula: ##STR2## in which R represents the radical C_(n) H_(2n+1), withn having a value preferably ranging from 3 to 8. The silicone oil ispreferably present in the composition in a proportion ranging from 30 to70%.

According to a preferred embodiment of the invention, the silicone oiland gum are used in the form of a homogeneous premix consisting of thesilicone gum solubilized in the silicone oil.

The composition according to the invention preferably also comprisespigments, in a proportion ranging from 0.5 to 15%, and more preferablyranging from 2 to 8%.

The pigments may be white or coloured and inorganic or organic.

The pigments used in the composition according to the invention may ormay not be coated.

U.S. Pat. No. 4,578,566, the disclosure of which is incorporated hereinby reference, describes a pretreatment of pigments in order to make themhydrophobic, as a solution in order to introduce large proportionsthereof into silicone-based compositions, and in order to ensure betterdispersion thereof in the composition. This pretreatment is carried outby coating the pigments with a polysiloxane. Obviously, thispretreatment increases not only the preparation time of the compositionsbut also their cost.

As has been mentioned above, a particular advantage of the inventionlies in the fact that the compositions according to the invention allowa homogeneous and stable dispersion to be obtained, even when pigmentswhich have not been precoated are used.

Among the pigments which may preferably be used, there may be mentioned,without any limiting effect, titanium dioxide (TiO₂), zinc oxide (ZnO),zirconium dioxide (ZrO₂), black, yellow, red and brown iron oxides,cerium dioxide (CeO₂) or alternatively the organic pigments known asbarium, strontium, calcium and aluminium lakes.

The composition according to the invention preferably contains 0 to 30%of fillers. These fillers may preferably be inorganic or synthetic andlamellar or non-lamellar.

Talc, mica, silica, kaolin, powders of nylon and of polyethylene,Teflon, starch, titanium mica, natural mother of pearl, boron nitrideand hollow microspheres such as Expancel from Nobel Industrie may bementioned.

The composition according to the invention may also compriseconstituents usually used in cosmetic compositions of this type. Theseconstituents are preferably chosen as a function of the desired cosmeticeffect for the final composition, such as the covering power, thetransparency, the matt quality and/or the satiny appearance.

There may be mentioned, without any limiting effects:

gelling agents, such as the modified clays known under the name bentone,which are sold by the company NL Industrie and used as they are orprepackaged in a gel; hydrophobic silica; waxes, for examplepolyethylene; aluminum fatty salts. The percentage of gelling agent inthe composition will be chosen depending on whether a supple or creamyformula is desired.

vitamins such as tocopherols and derivatives thereof, vitamin A andderivatives thereof, vitamin C and derivatives thereof such as the fattyesters, including the palmitate ester.

sunscreens such as octyl methoxycinnamate (Parsol MCX), 3-benzophenone(Uvinul M40), and butylmethoxydibenzoylmethane (Parsol 1789).

oily materials such as plant oils, synthetic esters, lecithin,fragrances and essential oils.

The processes for the manufacture of the compositions according to theinvention do not differ in any way from the processes conventionallyused in cosmetics and with which those skilled in the art are fullyfamiliar.

The compositions according to the invention may be in the form of aproduct for making up the skin, such as a foundation, a blusher, aneyeshadow or a lipstick, or even in the form of a hair product such as astyling make-up gel.

Examples of compositions according to the invention will now be given byway of example, without any limiting nature being implied.

EXAMPLE 1

Make-up gels having the following compositions (in g) were prepared:

    ______________________________________                                                    Compos. A                                                                             Compos. B  Compos. C                                      ______________________________________                                        A)  Polydimethylsiloxane                                                                        67.50     67.50    67.50                                        at a concentration                                                            of 12-14% in                                                                  cyclopentasiloxane                                                            (Q2-1401 from Dow)                                                        B)  TiO.sub.2 + iron oxides*                                                                    3.36      3.36     3.36                                     C)  cyclopentadimethyl-                                                                         9.50      9.50     --                                           siloxane                                                                  D)  Gelling agent                                                                 bentone gel IMP (NL                                                                         18.64     19.14    --                                           Industrie)                                                                    bentone gel VS-5 PC                                                                         --        28.14    28.14                                        Stearinerie Dubois)                                                       E)  Fillers                                                                       Expancel      1.00      1.00     1.00                                         microspheres                                                                  Teflon Ceri-dust                                                                            --        2.00     --                                       ______________________________________                                         *Non-coated pigments                                                     

A) and B) were mixed together with a spatula and were passed 3 timesthrough a cylinder mill. C), D) and E) were then added with moderatestirring.

Three formulae were obtained, which contained a large proportion ofsilicone-containing compounds and which made it possible to obtain,after spreading on the skin, a coloured and water-resistant make-up.

Although the pigments used were not precoated, the pigments were fullydispersed in the composition and the make-up obtained was homogeneous.

EXAMPLE 2

Self-tanning compositions having the following compositions (in g) wereprepared:

    ______________________________________                                                    Compos. D                                                                             Compos. E  Compos. F                                      ______________________________________                                        A)  Polydimethylsiloxane                                                                        67.50     67.50    67.50                                        at a concentration                                                            of 12-14% in                                                                  cyclopentasiloxane                                                            (Q2-1401)                                                                 B)  TiO.sub.2 + iron oxides*                                                                    3.36      3.36     3.36                                     C)  Crosslinked silicone                                                                        20.00     10.00    10.00                                        powder in a PDMS                                                              (KSG 16 from Shin                                                             Etsu)                                                                         bentone gel VS-5 PC                                                                         --        10.00    --                                           (Dubois)                                                                      Unitwix (United                                                                             --        --       --                                           Guardian)                                                                 D)  Polyvinylidene                                                                              1.00      1.00     1.00                                     E)  Silicone oils                                                                 Alkyldimethicone                                                                            --        --       5.00                                         X2-1731 (Dow)                                                                 Cyclopentadimethyl-                                                                         qs 100    qs 100   qs 100                                       siloxane                                                                  ______________________________________                                         *Non-coated pigments                                                     

Thickened gelled creams were obtained, which were easy and pleasant toapply, and which gave a homogeneous and uniform coloration of naturalappearance to the skin.

EXAMPLE 3

Water-resistant silicone-containing self-tanning compositions having thefollowing compositions (in g) were prepared:

    ______________________________________                                                         Compos. G                                                                              Compos. H                                           ______________________________________                                        A)  Silicone oil (AK 500,000                                                                         10.00      --                                              from Wacker)                                                                  Polydimethylsiloxane at a                                                                        6.64       12.30                                           concentration of 12-14% in                                                    cyclomethicone (Q2-1401 from                                                  Dow)                                                                          Polyphenylsiloxane at a                                                                          --         40.00                                           concentration of 15% in                                                       cyclopentadimethylsiloxane                                                    (Silbione 71634 from Rhone-                                                   Poulenc)                                                                  B)  TiO.sub.2 + iron oxides*                                                                         3.36       7.7                                         C)  Crosslinked silicone powder                                                                      20.00      10.00                                           (KSG 16 from Shin Etsu)                                                   D)  Gelling agent (Bentone gel                                                    VS38 from Rheox)   --         18.00                                       E)  Silicone-containing resin                                                                        --         5.00                                            beads (Tospearl 120 from                                                      Toshiba)                                                                  F)  Cyclopentadimethylsiloxane                                                                       60.00      qs 100                                      ______________________________________                                         *Non-coated pigments                                                     

Coloured and water-resistant self-tanning compositions were obtained inthe form of gels.

EXAMPLE 4

A lipstick having the following composition was prepared:

    ______________________________________                                        Polydimethylsiloxane at a concentration of                                                             70.00                                                12-14% in cyclomethicone (Q2-1401)                                            Crosslinked silicone powder in PDMS (KSG 16                                                            10.00                                                from Shin Etsu)                                                               Cyclopentadimethylsiloxane                                                                             10.00                                                Silicone-coated titanium oxide                                                                         2.83                                                 Silicone-coated iron oxides                                                                            4.70                                                 D&C red No. 7            0.47                                                 Titanium mica            2.00                                                 ______________________________________                                    

A fluid gelled cream of red-pink colour with an iridescent effect wasobtained, which was smooth upon application and had good staying power.

EXAMPLE 5

A screening tanning fluid having the following composition was prepared:

    ______________________________________                                        Polydimethylsiloxane at a concentration                                                                  70.00                                              of 12-14% in cyclomethicone (Q2-1401)                                         UV screening agents Parsol MCX from BASF                                                                 7.00                                               Hydroxy-4-methoxybenzophenone                                                                            2.00                                               FINSOLV TN (C.sub.12 -C.sub.15 alkyl benzoate) from Finetex                                              9.00                                               Jojoba oil                 1.00                                               α-tocopheryl acetate 1.00                                               Ethanol                    4.70                                               Fragrance                  0.30                                               Crosslinked silicone powder in PDMS (KSG 16                                                              10.00                                              from Shin Etsu)                                                               TiO.sub.2 + iron oxides (non-coated)                                                                     1.70                                               ______________________________________                                    

A shiny, smooth brown-coloured tanning fluid was obtained, which waseasy to apply and gave a homogeneous and uniform coloration of naturalappearance to the skin.

What is claimed is:
 1. A cosmetic composition comprising from 2% to 50%of at least one silicone gum, from 10% to 90% of at least one siliconeoil, from 0.5% to 15% of at least one pigment, and from 0 to 30% of atleast on filler, wherein said at least one silicone gum is of theformula: ##STR3## in which R1, R2, R5 and R6 each independentlyrepresents an alkyl radical having from 1 to 6 carbon atoms;R3 and R4each independently represents an alkyl radical having from 1 to 6 carbonatoms or an aryl radical; X represents an alkyl radical having from 1 to6 carbon atoms, a hydroxyl radical or a vinyl radical; and n and p areselected so as to give said silicone gum a viscosity of greater than100,000 mPa s, wherein said at least one silicone gum and said at leastone silicone oil are present in the form of a homogeneous premixconsisting of said at least one silicone gum solubilized in said atleast one silicone oil; wherein said composition is anhydrous andwater-resistant, and further wherein said composition has cosmeticproperties.
 2. A composition according to claim 1, wherein said at leastone silicone gum is present in an amount which ranges from 4% to 15% byweight relative to the total weight of said composition.
 3. Acomposition according to claim 2, wherein said at least one silicone gumis present in an amount which ranges from 6% to 9%, by weight relativeto the total weight of said composition.
 4. A composition according toclaim 1, wherein n and p have values ranging from 0 to
 5000. 5. Acomposition according to claim 4, wherein n and p have values rangingfrom 0 to
 3000. 6. A composition according to claim 1, wherein said atleast one silicone gum is a gum wherein:the substitutents R1 to R6 and Xrepresent a methyl group, p=0 and n=2700; the substitutents R1 to R6 andX represent a methyl group, p=0 and n=2300; the substitutents R1 to R6represent a methyl group, the substituent X represents a hydroxyl group,p=0 and n=2700.
 7. A composition according to claim 1, wherein said atleast one silicone oil is present in an amount which ranges from 30% to70%.
 8. A composition according to claim 1, wherein said at leastsilicone oil is a cyclomethicone, a polydimethylsiloxane of viscosityless than 100 mPa s, or an alkyldimethicone.
 9. A composition accordingto claim 1, wherein said at least one pigment is present in an amountwhich ranges from 2 to 8% by weight relative to the total weight of thecomposition.
 10. A composition according to claim 1, wherein said atleast one pigment is inorganic or organic and is coated or non-coated.11. A composition according to claim 1, wherein said at least onepigment is titanium dioxide, zinc oxide, zirconium dioxide, black,yellow, red or brown iron oxide, cerium dioxide, an organic pigment or amixture thereof.
 12. A composition according to claim 11, wherein saidorganic pigment is barium, strontium, calcium or aluminium lakes.
 13. Acomposition according to claim 1, which is in the form of a make-upproduct or a hair product.
 14. A composition according to claim 13,wherein said make-up product is a lipstick, a blusher, an eyeshadow or afoundation and said hair product is a styling make-up gel.
 15. Acomposition according to claim 1, wherein said at least one filler isinorganic or synthetic and lamellar or non-lamellar.
 16. A compositionaccording to claim 1, which further comprises at least one gellingagent, vitamin, sunscreen or oil material.